WO2000052068A1 - Procede de production de polyethylene - Google Patents

Procede de production de polyethylene Download PDF

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Publication number
WO2000052068A1
WO2000052068A1 PCT/US1999/004766 US9904766W WO0052068A1 WO 2000052068 A1 WO2000052068 A1 WO 2000052068A1 US 9904766 W US9904766 W US 9904766W WO 0052068 A1 WO0052068 A1 WO 0052068A1
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Prior art keywords
ether
process according
electron donor
methyl
ziegler
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PCT/US1999/004766
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English (en)
Inventor
Randal Ray Ford
William Albert Ames
Kenneth Alan Dooley
Jeffrey James Vanderbilt
Alan George Wonders
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Eastman Chemical Company
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Priority to EP99911105A priority Critical patent/EP1159315B1/fr
Priority to CNB998166065A priority patent/CN1168748C/zh
Priority to DE69933139T priority patent/DE69933139T2/de
Priority to KR1020017011101A priority patent/KR100582313B1/ko
Priority to PCT/US1999/004766 priority patent/WO2000052068A1/fr
Priority to JP2000602690A priority patent/JP2002538244A/ja
Priority to BR9917189-9A priority patent/BR9917189A/pt
Publication of WO2000052068A1 publication Critical patent/WO2000052068A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/04—Polymerisation in solution
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/18—Suspension polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/34—Polymerisation in gaseous state
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/602—Component covered by group C08F4/60 with an organo-aluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/607—Catalysts containing a specific non-metal or metal-free compound
    • C08F4/609—Catalysts containing a specific non-metal or metal-free compound organic
    • C08F4/6094—Catalysts containing a specific non-metal or metal-free compound organic containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/61—Pretreating the metal or compound covered by group C08F4/60 before the final contacting with the metal or compound covered by group C08F4/44
    • C08F4/612—Pretreating with metals or metal-containing compounds
    • C08F4/614—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof
    • C08F4/6143—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof halides of magnesium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/646—Catalysts comprising at least two different metals, in metallic form or as compounds thereof, in addition to the component covered by group C08F4/64
    • C08F4/6465—Catalysts comprising at least two different metals, in metallic form or as compounds thereof, in addition to the component covered by group C08F4/64 containing silicium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins

Definitions

  • the present invention relates to a polymerization process for the production of a polyethylene and films produced from the polyethylene.
  • Polyethylene polymers are well known and are useful in many applications.
  • linear polyethylene polymers possess properties which distinguish them from other polyethylene polymers, such as branched ethylene homopolymers commonly referred to as LDPE (low density polyethylene). Certain of these properties are described by Anderson et aL U.S. Patent No. 4,076,698.
  • a particularly useful polymerization medium for producing polyethylene polymers is a gas phase process. Examples of such are given in U.S. Patent Nos. 3,709,853; 4,003,712; 4,011,382; 4,302,566; 4,543,399; 4,882,400; 5,352,749 and 5,541,270 and Canadian Patent No. 991,798 and Belgian Patent No. 839,380.
  • Ziegler-Natta type catalyst systems for the polymerization of olefins are well known in the art and have been known at least since the issuance of U.S. Patent No. 3,113,115. Thereafter, many patents have been issued relating to new or improved Ziegler-Natta type catalysts. Exemplary of such patents are U.S. Patents Nos. 3,594,330; 3,676,415; 3,644,318; 3,917,575; 4,105,847; 4,148,754; 4,256,866; 4,298,713; 4,311,752; 4,363,904; 4,481,301 and Reissue 33,683.
  • halogenated hydrocarbons with Ziegler-Natta type polymerization catalysts in the production of polyethylene is disclosed in U.S. Patent No. 3,354,139 and European Patent Nos. EP 0 529 977 Bl and EP 0 703 246 Al. As disclosed, the halogenated hydrocarbons may reduce the rate of ethane formation, improve catalyst efficiency, or provide other effects.
  • halogenated hydrocarbons are monohalogen and polyhalogen substituted saturated or unsaturated aliphatic, alicyclic, or aromatic hydrocarbons having 1 to 12 carbon atoms.
  • exemplary aliphatic compounds include methyl chloride, methyl bromide, methyl iodide, methylene chloride, methylene bromide, methylene iodide, chloroform, bromoform, iodoform, carbon tetrachloride, carbon tetrabromide, carbon tetraiodide, ethyl chloride, ethyl bromide, 1,2-dichloroethane, 1,2-dibromoethane, methylchloroform, perchloroethylene and the like.
  • Exemplary alicyclic compounds include chlorocyclopropane, tetrachlorocyclopentane and the like.
  • Exemplary aromatic compounds include chlorobenzene, hexabromobenzene, benzotrichloride and the like. These compounds may be used individually or as mixtures thereof.
  • Electron donors typically known as Lewis Bases, when employed during the catalyst preparation step are referred to as internal electron donors.
  • Electron donors when utilized other than during the catalyst preparation step are referred to as external electron donors.
  • the external electron donor may be added to the preformed catalyst, to the prepolymer, and/or to the polymerization medium.
  • electron donors include carboxylic acids, carboxylic acid esters, alcohols, ethers, ketones, amines, amides, nitriles, aldehydes, thioethers, thioesters, carbonic esters, organosilicon compounds containing oxygen atoms, and phosphorus, arsenic or antimony compounds connected to an organic group through a carbon or oxygen atom.
  • the polymerization process of the present invention comprises the introduction into a polymerization medium containing ethylene and optionally other olefin(s), a Ziegler-Natta type polymerization catalyst containing at least one or more internal electron donor in an amount represented by a molar ratio of internal electron donor to transition metal compound of the Ziegler-Natta type catalyst of from 1 : 1 to about 1000: 1, trimethylalurj ⁇ dnum (TMA) as a co-catalyst, and at least one or more external electron donor compound containing at least one carbon-oxygen-carbon linkage (C-O-C) of Formula 1:
  • n ranges from 1 to 30;
  • R 1 and R 2 are independently selected from the group consisting of hydrogen, saturated and unsaturated aliphatic groups containing from 1 to 30 carbon atoms and from 0 to 30 heteroatoms of an element, or mixtures thereof, selected from Groups 13, 14, 15, 16 and 17 of the Periodic Table of Elements, and substituted and unsubstituted aromatic groups containing from 1 to 30 carbon atoms and from 0 to 30 heteroatoms of an element, or mixtures thereof selected from Groups 13, 14, 15, 16 and 17 of the Periodic Table of Elements;
  • R 3 and R 4 are linked and form part of a cyclic or polycyclic structure and are hydrocarbons independently selected from the group consisting of saturated and unsaturated aliphatic groups containing from 1 to 30 carbon atoms and from 0 to 30 heteroatoms of an element, or mixtures thereof, selected from Groups 13, 14, 15, 16 and 17 of the Periodic Table of Elements, and substituted and unsubstituted aromatic groups containing from 1 to 30 carbon atoms and from 0 to 30 heteroatoms of an element, or mixtures thereof, selected from Groups 13, 14, 15, 16 and 17 of the Periodic Table of Elements;
  • R is selected from the group consisting of substituted and unsubstituted aromatic groups containing from 1 to 30 carbon atoms and from 0 to 30 heteroatoms of an element, or mixtures thereof, selected from Groups 13, 14, 15, 16 and 17 of the Periodic Table of Elements;
  • R , R , R and R are independently selected from the group consisting of saturated and unsaturated aliphatic groups containing from 1 to
  • Mixtures of compounds of Formulas 1, 2, 3 and 4 can also be used as the external electron donor herein.
  • a halogenated hydrocarbon compound can be employed in the polymerization medium.
  • the external electron donor as defined herein and/or the TMA may be added to the polymerization medium in any manner.
  • the external electron donor as defined herein and/or the TMA may be added to the catalyst just prior to addition to the polymerization medium, or added separately from the catalyst to the polymerization medium in any manner known in the art.
  • the external electron donor as defined herein may optionally be premixed with the TMA co-catalyst.
  • a gas phase fluidized bed process is utilized for polymerization of the ethylene, it may be advantageous to add the external electron donor as defined herein prior to the heat removal means, e.g., the heat exchanger, to slow the rate of fouling of said heat removal means.
  • the present inventors have discovered an improved process for producing polyethylene.
  • the process involves the unexpected discovery of the use of a particular combination of a Ziegler-Natta catalyst containing at least one or more internal electron donor in an amount represented by a molar ratio of internal electron donor to transition metal compound of the Ziegler-Natta type catalyst of from 1: 1 to about 1000: 1, trimethylaluminum (TMA) co-catalyst and at least one or more external electron donor compound containing at least one carbon-oxygen-carbon linkage (C- O-C) of Formula 1:
  • TMA trimethylaluminum
  • C- O-C carbon-oxygen-carbon linkage
  • n ranges from 1 to 30;
  • R 1 and R 2 are independently selected from the group consisting of hydrogen, saturated and unsaturated aliphatic groups containing from 1 to 30 carbon atoms and from 0 to 30 heteroatoms of an element, or mixtures thereof, selected from Groups 13, 14, 15, 16 and 17 of the Periodic Table of Elements, and substituted and unsubstituted aromatic groups containing from 1 to 30 carbon atoms and from 0 to 30 heteroatoms of an element, or mixtures thereof selected from Groups 13, 14, 15, 16 and 17 of the Periodic Table of Elements;
  • R 3 and R 4 are linked and form part of a cyclic or polycyclic structure and are hydrocarbons independently selected from the group consisting of saturated and unsaturated aliphatic groups containing from 1 to 30 carbon atoms and from 0 to 30 heteroatoms of an element, or mixtures thereof, selected from Groups 13, 14, 15, 16 and 17 of the Periodic Table of Elements, and substituted and unsubstituted aromatic groups containing from 1 to 30 carbon atoms and from 0 to 30 heteroatoms of an element, or mixtures thereof, selected from Groups 13, 14, 15, 16 and 17 of the Periodic Table of Elements;
  • R 5 is selected from the group consisting of substituted and unsubstituted aromatic groups containing from 1 to 30 carbon atoms and from 0 to 30 heteroatoms of an element, or rnixtures thereof selected from Groups 13, 14, 15, 16 and 17 of the Periodic Table of Elements;
  • R 6 , R 7 , R 8 and R 9 are independently selected from the group consisting of saturated and unsaturated aliphatic groups containing from 1 to 30 carbon atoms and from 0 to 30 heteroatoms of an element, or mixtures thereof, selected from Groups 13, 14, 15, 16 and 17 of the Periodic Table of Elements, and substituted and unsubstituted aromatic groups containing from 1 to 30 carbon atoms and from 0 to 30 heteroatoms of an element, or mixtures thereof, selected from Groups 13, 14, 15, 16 and 17 of the Periodic Table of Elements.
  • Mixtures of compounds of Formulas 1, 2, 3 and 4 can also be used as the external electron donor herein.
  • R 1 and R 2 groups suitable for use herein are hydrogen, C ⁇ 3 o alkyl, C 2-3 o alkenyl, C 4 . 3 o dienyl, C 3-3 o cycloalkyl, C 3-30 cycloalkenyl, C 4-30 cyclodienyl, C6 -3 o aryl, C 7-30 aralkyl and C - 3 o alkaryl.
  • hydrocarbons containing from 1 to 30 carbon atoms and from 1 to 30 heteroatoms of an element, or mixtures thereof, from Groups 13, 14, 15, 16 and 17 of the Periodic Table of Elements such as, for example, B 1-30 borohydrocarbons, Si 1-3 o silahydrocarbons, P ⁇ -3 o phosphahydrocarbons, S O thiahydrocarbons, Cl ⁇ -3 o chlorohydrocarbons and halogenated hydrocarbons containing mixtures of halogens.
  • R 3 and R 4 hydrocarbon groups suitable for use herein are Ci.
  • Elements such as, for example, B 1-3 o borohydrocarbons, Si ⁇ -3 o silahydrocarbons, P ⁇ -3 o phosphahydrocarbons, Si -30 thiahydrocarbons, Cl ⁇ -3 o chlorohydrocarbons and halogenated hydrocarbons containing mixtures of halogens, where R 3 and R 4 are linked and form part of a cyclic or polycyclic structure.
  • R 5 group suitable for use herein are C6 -3 o aryl and C -3 o aralkyl.
  • substituted and unsubstituted aromatic hydrocarbons containing from 1 to 30 carbon atoms and from 1 to 30 heteroatoms of an element, or mixtures thereof from Groups 13, 14, 15, 16 and 17 of the Periodic Table of Elements such as, for example, B 1-3 o borohydrocarbons, Si 1-3 o silahydrocarbons, P 1-30 phosphahydrocarbons, S 1-3 o thiahydrocarbons, Cl ⁇ -3 o chlorohydrocarbons and halogenated hydrocarbons containing mixtures of halogens.
  • R 6 , R 7 , R 8 , and R 9 groups suitable for use herein are C1-30 alkyl, C -3 o alkenyl, C 4-30 dienyL C 3-30 cycloalkyl, C 3-3 o cycloalkenyl, C 4-3 o cyclodienyl, C ⁇ - 30 aryl, C 7-3 o aralkyl and C 7-3 o alkaryl.
  • hydrocarbons containing from 1 to 30 carbon atoms and from 1 to 30 heteroatoms of an element, or mixtures thereof, from Groups 13, 14, 15, 16 and 17 of the Periodic Table of Elements such as, for example, B ⁇ - 30 borohydrocarbons, Si 1-3 o silahydrocarbons, P 1-3 o phosphahydrocarbons, S1.30 thiahydrocarbons, CI1.30 chlorohydrocarbons and halogenated hydrocarbons containing mixtures of halogens.
  • R 1 -CH 2 -O-CH 2 -R 2 that may be used herein are compounds containing one C-O-C linkage such as alkyl, alkenyl, dienyl and aryl substituted compounds.
  • dimethyl ether diethyl ether; dipropyl ether; dibutyl ether; dipentyl ether; diisoamyl ether; dihexyl ether; dioctyl ether; dibenzyl ether; diallyl ether; allyl methyl ether; allyl ethyl ether; allyl benzyl ether; benzyl methyl ether; benzyl ethyl ether; butyl methyl ether; butyl ethyl ether; isoamyl methyl ether; isoamyl ethyl ether; isoamyl propyl ether; isoamyl butyl ether and the like.
  • hydrocarbons of Formula 1 containing heteroatoms from Groups 13, 14, 15, 16 and 17 of the Periodic Table of Elements are bis(trimethylsilylmethyl) ether; trimethylsilylmethyl methyl ether; bis(2,2,2- trifluoroethyl) ether; benzyl 3-bromopropyl ether; benzyl 3-bromo-2-chloropropyl ether; benzyl chloromethyl ether; butyl 2-chloroethyl ether; chloromethyl methyl ether; chloromethyl ethyl ether; dimethyl 2-methoxyethyl borate; dimethyl methoxymethyl borate; dimethoxy-2-methoxyethylborane; diphenyl-2- methoxyethylphosphine; diphenylmethoxymethylphosphine; 2-(2-thienyl)ethyl ethyl ether; 2-(2-thienyl)ethyl methyl ether
  • R 3 -O-R 4 are cyclic compounds where R 3 and R 4 are linked and form part of a cyclic or polycyclic structure such as, for example, ethylene oxide; propylene oxide; 1,2-epoxybutane; 2,3-epoxybutane; l,2-epoxybut-3-ene; cyclopentene oxide; trimethylene oxide; styrene oxide; 3,3-dimethyloxetane; furan; 2,3-dihydrofuran; 2,5-dihydrofi ⁇ ran; tetrahydrofuran; 2-methyltetrahydrofuran; 2,5-dimethyltetrahydrofuran; 4,5-dihydro- 2-methylfuran; 2-methylfuran; 2-ethylfuran; 2-tert-butylfuran; 2,5-dimethylfuran; 2,3-dimethylfuran; 1,2-pyran; 1,4-pyran; te
  • cyclic compounds containing more than one C-O-C linkage such as, for example, 2,5- dimethoxyfuran; 2-methoxyfuran; 3-methoxyfuran; 2-methoxytetrahydropyran; 3- methoxytetrahydropyran; 1,3-dioxolane; 2-methyl- 1,3-dioxolane; 2,2-dimethyl-l,3- dioxolane; 2-ethyl-2-methyl- 1,3-dioxolane; 2,2-tetramethylene- 1,3-dioxolane; 2,2- pentamethylene- 1,3-dioxolane; 2-vinyl- 1,3-dioxolane; 2-methoxy- 1,3-dioxolane; 1,4- dioxaspiro[4.4]non-6-ene; 1,4,9, 12-tetraoxadispiro(4.2.4.2)tetradecane; 1,3-dioxane; 1,4
  • hydrocarbons of Formula 2 containing heteroatoms from Groups 13, 14, 15, 16 and 17 of the Periodic Table of Elements are epichlorohydrin; 3-bromofuran;2-chloromethyl- 1,3-dioxolane; 4- chlorotetrahydropyran; tri-2- urylphosphine; 1-furfurylpyrrole; dimethyl 3- furylmethyl borate; 2-trimethylsily lfuran; 3-trimethylsilylfuran; 2-trimethylsilyl- 1,3- dioxolane; 2-(3-thienyl)- 1,3-dioxolane; 2-bromochloromethyl- 1,3-dioxolane; oxazole; 1,3,4-oxadiazole; 3,4-dichloro-l,2-epoxybutane; 3,4-dibromo-l,2- epoxybutane and the like.
  • R 5 -O-R 6 is compounds containing one C-O-C linkage such as alkyl, alkenyl, dienyl and aryl substituted aromatic compounds.
  • Specific examples are diphenyl ether; bis(2-tolyl) ether; bis(3-tolyl) ether; bis(l-naphthyl) ether; bis(2-naphthyl) ether; allyl phenyl ether; allyl 2-tolyl ether; allyl 3-tolyl ether; allyl 1-naphthyl ether; allyl 2-naphthyl ether; benzyl phenyl ether; benzyl 2-tolyl ether; benzyl 3-tolyl ether; benzyl 1- naphthyl ether; benzyl 2-naphthyl ether; ethyl phenyl ether; ethyl
  • hydrocarbons of Formula 3 containing heteroatoms from Groups 13, 14, 15, 16 and 17 of the Periodic Table of Elements are 2-ethoxy-l-methylpyrrole; 3-methoxy-l-methylpyrrole; 2-ethoxythiophene; 3- methoxythiophene; 3-methoxy-l-methylpyrazole; 4-methoxy- 1-methylpyrazole; 5- methoxy- 1-methylpyrazole; 2- methoxy- 1-methylimidazole; 4-methoxy- 1- methylimidazole; 5-methoxy- 1-methylimidazole; 3-methoxy- 1-phenylpyrazole; 4- methoxy- 1-phenylpyrazole; 5-methoxy- 1-phenylpyrazole; 2-methoxy-l- phenylimidazole; 4-methoxy- 1-phenylimidazole; 5-methoxy- 1-phenylimidazole; 4- methoxy- 1-methyl- 1,2,3-triazole; 5-methoxy- 1-methyl- 1,2,
  • R 7 -O(-R 8 -O) ⁇ -R 9 compounds containing more than one C-O-C linkage are alkyl, alkenyl, dienyl and aryl substituted compounds where n ranges from 1 to 30.
  • Also exemplary of compounds of Formula 4 contaiiiing heteroatoms from Groups 13, 14, 15, 16 and 17 of the Periodic Table of Elements are ethylene glycol bis(trimethylsilylmethyl) ether; di( ethylene glycol) methyl trimethylsilyl ether; tris(2-methoxyethyl) borate; ethylene glycol chloromethyl bromomethyl ether and the like.
  • Preferred for use herein as external electron donors are dimethyl ether; diethyl ether; dipropyl ether; dibutyl ether; diisoamyl ether; dibenzyl ether; butyl methyl ether; butyl ethyl ether; chloromethyl methyl ether; trimethylsilylmethyl methyl ether; bis(trimethylsilylmethyl) ether; bis(2,2,2-trifluoroethyl) ether; ethylene oxide; propylene oxide; 1,2-epoxybutane; cyclopentene oxide; epichlorohydrin; furan; 2,3- dihydrofuran; 2,5-dihydrofuran; tetrahydrofuran; 2-methyltetrahydrofuran; 2,5- dimethyltetrahydrofiiran; 2-methylfuran; 2,5- ⁇ methylfuran; tetrahydropyran; 1,2- epoxybut-3-ene; styrene oxide; 2-ethylfuran
  • the external electron donor are tetrahydrofuran, diethyl ether, dipropyl, methyl propyl ether, dibutyl ether, dioctyl ether, trimethylene oxide and tetrahydropyran.
  • the polymerization process of the present invention may be carried out using any suitable process.
  • a particularly desirable method for producing polyethylene polymers according to the present invention is a gas phase polymerization process preferably utilizing a fluidized bed reactor.
  • This type reactor and means for operating the reactor are well known and completely described in U.S Patents Nos. 3,709,853; 4,003,712; 4,011,382; 4,012,573; 4,302,566; 4,543,399; 4,882,400; 5,352,749; 5,541,270; Canadian Patent No. 991,798 and Belgian Patent No. 839,380.
  • These patents disclose gas phase polymerization processes wherein the polymerization medium is either mechanically agitated or fluidized by the continuous flow of the gaseous monomer and diluent. The entire contents of these patents are incorporated herein by reference.
  • the polymerization process of the present invention may be effected as a continuous gas phase process such as a fluid bed process.
  • a fluid bed reactor for use in the process of the present invention typically comprises a reaction zone and a so-called velocity reduction zone.
  • the reaction zone comprises a bed of growing polymer particles, formed polymer particles and a minor amount of catalyst particles fluidized by the continuous flow of the gaseous monomer and diluent to remove heat of polymerization through the reaction zone.
  • some of the recirculated gases may be cooled and compressed to form liquids that increase the heat removal capacity of the circulating gas stream when readmitted to the reaction zone.
  • a suitable rate of gas flow may be readily determined by simple experiment.
  • Make up of gaseous monomer to the circulating gas stream is at a rate equal to the rate at which particulate polymer product and monomer associated therewith is withdrawn from the reactor and the composition of the gas passing through the reactor is adjusted to maintain an essentially steady state gaseous composition within the reaction zone.
  • the gas leaving the reaction zone is passed to the velocity reduction zone where entrained particles are removed. Finer entrained particles and dust may be removed in a cyclone and/or fine filter.
  • the gas is passed through a heat exchanger wherein the heat of polymerization is removed, compressed in a compressor and then returned to the reaction zone.
  • the reactor temperature of the fluid bed process herein ranges from about 30°C to about 110°C.
  • the reactor temperature is operated at the highest temperature that is feasible taking into account the sintering temperature of the polymer product within the reactor.
  • the process of the present invention is suitable for the production of homopolymers of ethylene and or copolymers, terpolymers, and the like, of ethylene and at least one or more other olefins.
  • the olefins are alpha-olefins.
  • the olefins for example, may contain from 3 to 16 carbon atoms.
  • Particularly preferred for preparation herein by the process of the present invention are linear polyethylenes.
  • Such linear polyethylenes are preferably linear homopolymers of ethylene and linear copolymers of ethylene and at least one alpha-olefin wherein the ethylene content is at least about 70% by weight of the total monomers involved.
  • Exemplary alpha- olefins that may be utilized herein are propylene, 1-butene, 1-pentene, 1-hexene, 1- heptene, 1-octene, 4-methylpent-l-ene, 1-decene, 1-dodecene, 1-hexadecene and the like.
  • polyenes such as 1,3-hexadiene, 1,4-hexadiene, cyclop entadiene, dicyclopentadiene, 4-vinylcyclohex-l-ene, 1,5-cyclooctadiene, 5- vinylidene-2-norbornene and 5-vinyl-2-norbornene, and olefins formed in situ in the polymerization medium.
  • olefins are formed in situ in the polymerization medium, the formation of linear polyethylenes containing long chain branching may occur.
  • the polymerization reaction of the present invention is carried out in the presence of a Ziegler-Natta type catalyst.
  • the catalyst can be introduced in any manner known in the art.
  • the catalyst can be introduced directly into the polymerization medium in the form of a solution, a slurry or a dry free flowing powder.
  • the catalyst can also be used in the form of a deactivated catalyst, or in the form of a prepolymer obtained by contacting the catalyst with one or more olefins in the presence of a co-catalyst.
  • the Ziegler-Natta type catalyst utilized contains at least one or more internal electron donor.
  • the Ziegler-Natta type catalysts used herein there is incorporated at least one or more internal electron donors.
  • the internal electron donor is incorporated in an amount represented by a molar ratio of internal electron donor to transition metal compound of the Ziegler-Natta type catalyst of from 1: 1 to about 1000:1.
  • the Ziegler-Natta catalysts are well known in the industry.
  • the Ziegler-Natta catalysts in the simplest form are comprised of a transition metal compound and an organometallic co-catalyst compound.
  • the metal of the transition metal compound is a metal of Groups 4, 5, 6, 7, 8, 9 and 10 of the Periodic Table of the Elements, as published in "Chemical and Engineering News", 63(5), 27, 1985. In this format, the groups are numbered 1-18.
  • Exemplary of such transition metals are titanium, zirconium, vanadium, chromium, manganese, iron, cobalt, nickel, and the like, and mixtures thereof.
  • the transition metal is selected from the group consisting of titanium, zirconium, vanadium and chromium, and in a still further preferred embodiment, the transition metal is titanium.
  • the Ziegler-Natta catalyst can optionally contain magnesium and chlorine. Such magnesium and chlorine containing catalysts may be prepared by any manner known in the art.
  • Any internal electron donor can be utilized in preparing the Ziegler-Natta catalyst. Illustrative of the internal electron donors are hydrocarbons containing from 1 to 50 carbon atoms and from 1 to 30 heteroatoms of an element, or mixtures thereof, selected from Groups 14, 15, 16 and 17 of the Periodic Table of Elements.
  • Suitable internal electron donor compounds are, for example, ethers, thioethers, ainines, esters, thioesters, amides, anhydrides, acid halides, aldehydes, ketones, alcohols, nitriles, phosphines, silanes, carboxylic acids and the like.
  • ethers useful as internal electron donors are dimethyl ether; diethyl ether; dipropyl ether; diisopropyl ether; dibutyl ether; dipentyl ether; dihexyl ether; dioctyl ether; diisoamyl ether; di-tert-butyl ether; diphenyl ether; dibenzyl ether; divinyl ether; diallyl ether; dicyclopropyl ether; dicyclopentyl ether; dicyclohexyl ether; bis(2,2,2-trifluoroethyl) ether; allyl methyl ether; allyl ethyl ether; allyl cyclohexyl ether; allyl phenyl ether; allyl benzyl ether; allyl 2-tolyl ether; allyl 3-tolyl ether; allyl 4-tolyl ether; benzyl methyl ether; benzyl
  • Exemplary of thioethers useful as internal electron donors are dimethyl sulfide; diethyl sulfide; dipropyl sulfide; diisopropyl sulfide; dibutyl sulfide; dipentyl sulfide; dihexyl sulfide; dioctyl sulfide; diisoamyl sulfide; di-tert-butyl sulfide; diphenyl sulfide; dibenzyl sulfide; divinyl sulfide; diallyl sulfide; dipropargyl sulfide; dicyclopropyl sulfide; dicyclopentyl sulfide; dicyclohexyl sulfide; allyl methyl sulfide; allyl ethyl sulfide; allyl cyclohexyl sulfide; allyl
  • amines useful as internal electron donors are methylamine; ethylamine; propylarnine; isopropylamine; butylamine; isobutylamine; amylamine; isoamylamine; octylamine; cyclohexylamine; aniline; dime&ylamine; diethylamine; dipropylamine; diisopropylamine; dibutylamine; dhsobutylamine; diamylamine; dusoamylamine; dioctylamine; dicyclohexylamine; trimemylamine; triethylamine; tripropylamine; trusopropylamine; tributylamine; trusobutylamine; triamylamine; tr ⁇ soamylamine; trioctylamine; tricyclohexylamine; N-memylaniline; N-ethylaniline; N-propylani
  • esters useful as internal electron donors are methyl formate; methyl acetate; ethyl acetate; vinyl acetate; propyl acetate; butyl acetate; isopropyl acetate; isobutyl acetate; octyl acetate; cyclohexyl acetate; ethyl propionate; ethyl valerate; methyl chloroacetate; ethyl dichloroacetate, methyl methacrylate; ethyl crotonate; ethyl pivalate; methyl benzoate; ethyl benzoate; propyl benzoate; butyl benzoate; isobutyl benzoate; isopropyl benzoate; octyl benzoate; cyclohexyl benzoate; phenyl benzoate; benzyl benzoate; methyl 2-methylbenzoate; ethyl 2- methylbenzoate
  • thioesters useful as internal electron donors are methyl thiolacetate; ethyl thiolacetate; propyl thiolacetate; isopropyl thiolacetate; butyl thiolacetate; isobutyl thiolacetate; amyl thiolacetate; isoamyl thiolacetate; octyl thiolacetate; cyclohexyl thiolacetate; phenyl thiolacetate; 2-chloroethyl thiolacetate; 3-chloropropyl thiolacetate; methyl thiobenzoate; ethyl thiobenzoate; propyl thiobenzoate; isopropyl thiobenzoate; butyl thiobenzoate; isobutyl thiobenzoate; amyl thiobenzoate; isoamyl thiobenzoate; octyl thiobenzoate; cyclohexyl thiobenzoate
  • amides useful as internal electron donors are formamide; acetamide; propionamide; isobutyramide; trimethylacetamide; hexanoamide; octadecanamide; cyclohexanecarboxamide; 1-adamantanecarboxamide; acrylamide; methacrylamide; 2-fluoroacetamide; 2-chloroacetamide; 2-bromoacetamide; 2,2- dichloroacetamide; 2,2,2-trifluoroacetamide; 2,2,2-trichloroacetamide; 2- chloropropionamide; benzamide; N-methylformamide; N-ethylformamide; N- propylformamide; N-butylformamide; N-isobutylformamide; N-amylformamide; N- cyclohexylformamide; formanilide; N-methylacetamide; N-ethylacetamide; N- propylacetamide; N-butylacetamide; N-isobutylacetamide;
  • anhydrides useful as internal electron donors are acetic anhydride; propionic anhydride; butyric anhydride; isobutyric anhydride; valeric anhydride; trimethylacetic anhydride; hexanoic anhydride; heptanoic anhydride; decanoic anhydride; lauric anhydride; myristic anhydride; palmitic anhydride; stearic anhydride; docosanoic anhydride; crotonic anhydride; methacrylic anhydride; oleic anhydride; linoleic anhydride; chloroacetic anhydride; iodoacetic anhydride; dichloroacetic anhydride; trifluoroacetic anhydride; chlorodifluoroacetic anhydride; trichloroacetic anhydride; pentafluoropropionic anhydride; heptafluorobutyric anhydride; succinic anhydride;
  • Exemplary of acid halides useful as internal electron donors are acetyl chloride; acetyl bromide; chloroacetyl chloride; dichloroacetyl chloride; trichloroacetyl chloride; trifluoroacetyl chloride; tribromoacetyl chloride; propionyl chloride; propionyl bromide; butyryl chloride; isobutyryl chloride; trimethylacetyl chloride; 3-cyclopentylpropionyl chloride; 2-chloropropionyl chloride; 3- chloropropionyl chloride; tert-butylacetyl chloride; isovaleryl chloride; hexanoyl chloride; heptanoyl chloride; decanoyl chloride; lauroyl chloride; myristoyl chloride; palmitoyl chloride; stearoyl chloride; oleoyl chloride; cyclopentanecarbonyl chloride;
  • aldehydes useful as internal electron donors are formaldehyde; acetaldehyde; propionaldehyde; isobutyraldehyde; trimethylacetaldehyde; butyraldehyde; 2-methylbutyraldehyde; valeraldehyde; isovaleraldehyde; hexanal; 2- ethylhexanal; heptaldehyde; decyl aldehyde; crotonaldehyde; acrolein; methacrolein; 2-ethylacrolein; chloroacetaldehyde; iodoacetaldehyde; dichloroacetaldehyde; trifluoroacetaldehyde; chlorodifluoroacetaldehyde; trichloroacetaldehyde; pentafluoropropionaldehyde; heptafluorobutyraldehyde; phenylace
  • ketones useful as internal electron donors are acetone; 2- butanone; 3-methyl-2-butanone; pinacolone; 2-pentanone; 3-pentanone; 3-methyl-2- pentanone; 4-methyl- 2-pentanone; 2-methyl-3-pentanone; 4,4-dimethyl-2-pentanone; 2,4-dimethyl-3-pentanone; 2,2,4,4-tetramethyl-3-pentanone; 2-hexanone; 3- hexanone; 5-methyl-2-hexanone; 2-methyl-3-hexanone; 2-heptanone; 3-heptanone; 4- heptanone; 2-methyl-3-heptanone; 5-methyl-3-heptanone; 2,6-dimethyl-4-heptanone; 2-octanone; 3-octanone; 4-octanone; acetophenone; benzophenone; mesityl oxide; hexafluoroacetone; perfluoro-2-butanone; 1,1,
  • alcohols useful as internal electron donors are methanol; ethanol; propanol; isopropanol; butanol; isobutanol; hexanol; heptanol; octanol; dodecanol; octadecyl alcohol; 2-ethylhexyl alcohol; benzyl alcohol; cumyl alcohol; oleyl alcohol; diphenyl methanol; triphenyl methanol; phenol; cresol; ethylphenol; propylphenol; cumylphenol; naphthol; cyclopentanol; cyclohexanol and the like.
  • nitriles useful as internal electron donors are acetonitrile; propionitrile; butyronitrile; isobutyronitrile; valeronitrile; isovaleronitrile; trimethylacetomtrile; hexanenitrile; heptanenitrile; heptyl cyanide; octyl cyanide; undecanenitrile; malononitrile; succinonitrile; glutaronitrile; adiponitrile; sebaconitrile; allyl cyanide; acrylonitrile; crotononitrile; methacrylonitrile; fumaronitrile; tetracyanoethylene; cyclopentanecarbonitrile; cyclohexanecarbonitrile; dichloroacetonitrile; fluoroacetonitrile; trichloroacetonitrile; benzonitrile; benzyl cyanide; 2-methylbenzyl cyanide; 2-chlorobenzonitrile;
  • phosphines useful as internal electron donors are trimethylphosphine; triethylphosphine; trimethyl phosphite; triethyl phosphite; hexamethylphosphorus triamide; hexamethylphosphoramide; tripiperidinophosphine oxide; triphenylphosphine; tri-/ olylphosphine; tri-r ⁇ -tolylphosphine; tri-o- tolylphosphine; methyldiphenylphosphine; ethyldiphenylphosphine; isopropyldiphenylphosphine; allyldiphenylphosphine; cyclohexyldiphenylphosphine; benzyldiphenylphosphine; di-tert-butyl dimethylphosphoramidite; di-tert-butyl diethylphosphoramidite; di-tert-butyl diisopropyl
  • silanes useful as internal electron donors are tetramethyl orthosilicate; tetraethyl orthosuicate; tetrapropyl orthosuicate; tetrabutyl orthosuicate; trichloromethoxysilane; trichloroethoxysilane; trichloropropoxysilane; trichloroisopropoxysilane; trichlorobutoxysilane; trichloroisobutoxysilane; dichlorodimethoxysilane; dichlorodiethoxysilane; dichlorodipropoxysilane; dichlorodiisopropoxysilane; dichlorodibutoxysilane; dichlorodiisobutoxysilane; chlorotrimethoxysilane; chlorotriethoxysilane; chlorotripropoxysilane; chlorotriisopropoxysilane; chlorotributoxysilane; chlorotriis
  • carboxylic acids useful as internal electron donors are formic acid; acetic acid; propionic acid; butyric acid; valeric acid; hexanoic acid; heptanoic acid; octanoic acid; nonanoic acid; decanoic acid; lauric acid; myristic acid; palmitic acid; stearic acid; eicosanoic acid; heneicosanoic acid; heptacosanoic acid; isobutyric acid; 2-ethylbutyric acid; trimethylacetic acid; 2-methylbutyric acid; 2,2- dimethylbutyric acid; oxalic acid; malonic acid; methylmalonic acid; ethylmalonic acid; butylmalonic acid; dimethylmalonic acid; succinic acid; 2-methylsuccinic acid; 2,2-dimethylsuccinic acid; 2-ethyl-2-methylsuccinic acid; 2,3-dimethylsuccinic acid; gluta
  • 4-fluorobenzoic acid 2-ethoxybenzoic acid; 3-ethoxybenzoic acid; 4-ethoxybenzoic acid; 2-methoxybenzoic acid; 3-methoxybenzoic acid; 4-methoxybenzoic acid; 2- ethylbenzoic acid; 3-ethylbenzoic acid; 4-ethylbenzoic acid; 4-vinylbenzoic acid; 2- propylbenzoic acid; 2-isopropylbenzoic acid; 2-butylbenzoic acid; 2-isobutylbenzoic acid; 2-tert-butylbenzoic acid and the like.
  • the co-catalyst added to the polymerization medium of the present invention is trimemylaluminum (TMA).
  • the organometallic co-catalyst compound used to form the prepolymer can be any organometallic compound containing a metal of Groups 1, 2, 11, 12, 13 and 14 of the above described Periodic Table of the Elements. Exemplary of such metals are lithium, magnesium, copper, zinc, boron, silicon and the like.
  • TMA is still utilized as the co-catalyst in the polymerization medium.
  • the catalyst system may contain other conventional components in addition to the internal electron donors, the transition metal component, the external electron donors defined herein and the TMA co-catalyst component.
  • the internal electron donors for example, there may be added any magnesium compound known in the art, any halogenated hydrocarbon(s), and the like.
  • the Ziegler-Natta catalyst may be prepared by any method known in the art.
  • the catalyst can be in the form of a solution, a slurry or a dry free flowing powder.
  • the amount of Ziegler-Natta catalyst used is that which is sufficient to allow production of the desired amount of the polyethylene.
  • TMA is added to the polymerization medium in any amount sufficient to effect production of the desired polyethylene. It is preferred to incorporate the TMA in a molar ratio of TMA to transition metal component of the Ziegler-Natta catalyst ranging from about 1: 1 to about 100: 1. In a more preferred embodiment, the molar ratio of TMA to transition metal component ranges from about 1: 1 to about 50: 1.
  • the external electron donor is added in any manner.
  • the external electron donor may be added to the preformed catalyst, to the prepolymer during the prepolymerization step, to the preformed prepolymer and/or to the polymerization medium.
  • the external electron donor may optionally be premixed with the TMA co- catalyst.
  • the external electron donor is added in any amount sufficient to effect production of the desired polyethylene. It is preferred to incorporate the external electron donor in a molar ratio of external electron donor to transition metal component of the Ziegler-Natta catalyst ranging from about 0.01: 1 to about 100: 1. In a more preferred embodiment, the molar ratio of external electron donor to transition metal component ranges from about 0.1 : 1 to about 50:1.
  • any halogenated hydrocarbon including those mentioned hereinbefore, and preferably, chloroform.
  • the molar ratio of halogenated hydrocarbon to transition metal component of the Ziegler-Natta catalyst ranges preferably from about 0.001: 1 to about 1: 1.
  • the molecular weight of the polyethylene produced by the present invention can be controlled in any known manner, for example, by using hydrogen. The molecular weight control may be evidenced by an increase in the melt index (I 2 ) of the polymer when the molar ratio of hydrogen to ethylene in the polymerization medium is increased.
  • the polyethylenes of the present invention may be fabricated into films by any technique known in the art. For example, films may be produced by the well known cast film, blown film and extrusion coating techniques.
  • polyethylenes may be fabricated into other articles of manufacture, such as molded articles, by any of the well known techniques.
  • the invention will be more readily understood by reference to the following examples. There are, of course, many other forms of this invention which will become obvious to one skilled in the art, once the invention has been fully disclosed, and it will accordingly be recognized that these examples are given for the purpose of illustration only, and are not to be construed as limiting the scope of this invention in any way.
  • the polymerization process utilized in the Examples is carried out in a fluidized-bed reactor for gas-phase polymerization, consisting of a vertical cylinder of diameter 0.9 meters and height 6 meters and surmounted by a velocity reduction chamber.
  • the reactor is provided in its lower part with a fluidization grid and with an external line for recycling gas, which connects the top of the velocity reduction chamber to the lower part of the reactor, at a point below the fluidization grid.
  • the recycling line is equipped with a compressor for circulating gas and a heat transfer means such as a heat exchanger.
  • the reactor contains a fluidized bed consisting of a polyethylene powder made up of particles with a weight- average diameter of about 0.5 mm to about 1.4 mm.
  • the gaseous reaction mixture which contains ethylene, olefin comonomer, hydrogen, nitrogen and minor amounts of other components, passes through the fluidized bed under a pressure ranging from about 290 psig to about 300 psig with an ascending fluidization speed, referred to herein as fluidization velocity, ranging from about 1.8 feet per second to about 2.0 feet per second.
  • a Ziegler-Natta catalyst containing an internal electron donor is introduced mtermittently into the reactor.
  • the said catalyst contains magnesium, chlorine, titanium and an internal electron donor.
  • the rate of introduction of the catalyst into the reactor is adjusted for each given set of conditions in achieving the desired production rate.
  • a solution of trimethylaluminum (TMA) in n-hexane is introduced continuously into the line for recycling the gaseous reaction mixture, at a point situated downstream of the heat transfer means.
  • the feed rate of TMA is expressed as a molar ratio of TMA to titanium (TMA/Ti), and is defined as the ratio of the TMA feed rate (in moles of TMA per hour) to the catalyst feed rate (in moles of titanium per hour).
  • a solution of chloroform (CHC1 3 ) in n-hexane, at a concentration of about 0.5 weight percent, is introduced continuously into the line for recycling the gaseous reaction rnixture.
  • the feed rate of CHC1 3 is expressed as a molar ratio of CHC1 3 to titanium (CHC1 3 /Ti), and is defined as the ratio of the CHC1 3 feed rate (in moles of CHC1 3 per hour) to the catalyst feed rate (in moles of titanium per hour).
  • the feed rate of external electron donor (eED) is expressed as a molar ratio of eED to titanium (eED/Ti), and is defined as the ratio of the eED feed rate (in moles of eED per hour) to the catalyst feed rate (in moles of titanium per hour).
  • the productivity of the catalyst is the ratio of pounds of polyethylene produced per pound of catalyst added to the reactor.
  • the activity of the catalyst is expressed as grams of polyethylene per millimole titanium per hour per bar of ethylene pressure.
  • EXAMPLE 2 Preparation of LLDPE with TMA as Co-Catalyst and with Dibutyl Ether as External Electron Donor Utilizing a Ziegler-Natta Catalyst Containing Dibutylphthalate as Internal Electron Donor.
  • the process of Example 1 is followed with the exception that dibutyl ether is added as the external electron donor and the Ziegler-Natta catalyst contains dibutvlphthalate as the internal electron donor.
  • a linear polyethylene is obtained.
  • Example 1 The process of Example 1 is followed with the exception that methyl phenyl ether is added as the external electron donor and the Ziegler-Natta catalyst contains tetraethylorthosilicate as the internal electron donor. A linear polyethylene is obtained.
  • EXAMPLE 4 Preparation of LLDPE with TMA as Co-Catalyst and with 1.3-Dimethoxypropane as External Electron Donor Utilizing a Ziegler-Natta Catalyst Containing Ethanol as Internal Electron Donor.
  • Example 5 The process of Example 1 is followed with the exception that 1,3- dimethoxypropane is added as the external electron donor and the Ziegler-Natta catalyst contains ethanol as the internal electron donor. A linear polyethylene is obtained.
  • EXAMPLE 5 The process of Example 1 is followed with the exception that 1,3- dimethoxypropane is added as the external electron donor and the Ziegler-Natta catalyst contains ethanol as the internal electron donor. A linear polyethylene is obtained. EXAMPLE 5
  • Example 1 The process of Example 1 is followed with the exception that the Ziegler- ⁇ atta catalyst contains NN-dimethylformamide as the internal electron donor. A linear polyethylene is obtained.
  • EXAMPLE 6 Preparation of LLDPE with TMA as Co-Catalyst and with tert-Butyl Methyl Ether as External Electron Donor Utilizing a Ziegler- ⁇ atta Catalyst Containing Hexamethylphosphorus triamide as Internal Electron Donor.
  • the process of Example 1 is followed with the exception that tert-butyl methyl ether is added as the external electron donor and the Ziegler-Natta catalyst contains hexamethylphosphorus triamide as the internal electron donor.
  • a linear polyethylene is obtained.
  • Example 1 The process of Example 1 is followed with the exception that tert-butyl methyl ether is added as the external electron donor and the Ziegler- ⁇ atta catalyst contains N,N-dusopropylaniline as the internal electron donor. A linear polyethylene is obtained.
  • Example 1 The process of Example 1 is followed with the exception that diethyl ether is added as the external electron donor and the Ziegler- ⁇ atta catalyst contains trifluoroacetaldehyde as the internal electron donor. A linear polyethylene is obtained.
  • Example 1 Internal Electron Donor.
  • diisopropyl ether is added as the external electron donor and the Ziegler- ⁇ atta catalyst contains pinacolone as the internal electron donor.
  • pinacolone is obtained.
  • Example 1 The process of Example 1 is followed with the exception that THF is added as the external electron donor and the Ziegler-Natta catalyst contains acetonitrile as the internal electron donor. A linear polyethylene is obtained.
  • Films can be readily prepared from the polyethylenes of the present invention by any method known in the art for producing films.
  • Articles such as molded items can also be prepared from the polyethylenes of the present invention.

Abstract

Cette invention se rapporte à un nouveau procédé de production d'homopolymères et de copolymères d'éthylène, qui consiste à mettre en contact de l'éthylène et/ou de l'éthylène et au moins une ou plusieurs autres oléfines dans des conditions de polymérisation avec un catalyseur de type Ziegler-Natta contenant au moins un ou plusieurs donneurs d'électrons internes, du triméthylaluminium et au moins un ou plusieurs donneurs d'électrons externes contenant au moins une liaison carbone-oxygène-carbone (C-O-C) choisie dans le groupe constitué par un composé de formule (1) (R1-CH2-O-CH2-R2), un composé de formule (2), un composé de formule (3) (R5-O-R6), et un composé de formule (4) (R?7-O(-R8-O)¿n-R9). Cette invention concerne également des films et des articles ainsi produits.
PCT/US1999/004766 1999-03-03 1999-03-03 Procede de production de polyethylene WO2000052068A1 (fr)

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EP99911105A EP1159315B1 (fr) 1999-03-03 1999-03-03 Procede de production de polyethylene
CNB998166065A CN1168748C (zh) 1999-03-03 1999-03-03 制备聚乙烯的方法
DE69933139T DE69933139T2 (de) 1999-03-03 1999-03-03 Verfahren zur herstellung von polyethylen
KR1020017011101A KR100582313B1 (ko) 1999-03-03 1999-03-03 폴리에틸렌의 제조 방법
PCT/US1999/004766 WO2000052068A1 (fr) 1999-03-03 1999-03-03 Procede de production de polyethylene
JP2000602690A JP2002538244A (ja) 1999-03-03 1999-03-03 ポリエチレンの製造方法
BR9917189-9A BR9917189A (pt) 1999-03-03 1999-03-03 Processo para polimerizar etileno e/ou etileno epelo menos uma ou mais outras olefinas, pelìcula,e, artigo

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WO2005103094A1 (fr) * 2004-04-07 2005-11-03 Union Carbide Chemicals & Plastics Technology Corporation Compositions de procatalyseur a polymerisation olefinique et procede de preparation
WO2011107371A1 (fr) * 2010-03-04 2011-09-09 Basell Poliolefine Italia Srl Composants de catalyseur pour la polymérisation d'oléfines
WO2011107370A1 (fr) * 2010-03-04 2011-09-09 Basell Poliolefine Italia Srl Composants catalytiques pour la polymérisation des oléfines
CN103214601A (zh) * 2007-08-24 2013-07-24 陶氏环球技术有限责任公司 不含硅烷的自限制催化剂组合物
CN107778392A (zh) * 2016-08-31 2018-03-09 中国石油化工股份有限公司 一种用于乙烯聚合的催化剂组分及其制备方法和催化剂
DE10392773B4 (de) * 2002-06-06 2021-07-01 China Petroleum And Chemical Corporation Eine feste Katalysatorkomponente für die Polymerisation von Ethylen, Herstellung derselben und ein Katalysator diese enthaltend

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DE69919222T2 (de) * 1999-03-03 2004-12-30 Eastman Chemical Co., Kingsport Verfahren zur herstellung von polyethylen
JP5283808B2 (ja) * 2000-03-30 2013-09-04 住友化学株式会社 エチレン重合用触媒およびエチレン重合体の製造方法
AU2003292199A1 (en) * 2002-12-18 2004-07-09 Basell Poliolefine Italia S.P.A. Catalyst components for the polymerization of olefins
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CN102286118B (zh) * 2010-06-18 2013-02-27 中国石油化工股份有限公司 一种用于烯烃聚合的含钛的固体催化剂组分及催化剂
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EP1159315A1 (fr) 2001-12-05
DE69933139D1 (de) 2006-10-19
CN1348472A (zh) 2002-05-08
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